The oxidation of peroxide by disordered metal oxide water oxidation catalysts: a measurement of thermodynamic stability "by proxy"

Sabri, Mayada, King, Hannah J., Gummow, Rosalind J., Malherbe, Francois, and Hocking, Rosalie K. (2018) The oxidation of peroxide by disordered metal oxide water oxidation catalysts: a measurement of thermodynamic stability "by proxy". ChemPlusChem, 83 (7). pp. 620-629.

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It is often noted that disordered materials have different chemical properties to their more "ordered" cousins. Quantifying these effects in terms of thermodynamics is challenging in part because disordered materials can be difficult to characterise and are frequently relatively unstable. During the course of our experiments to understand the effects of disorder in catalysts for water oxidation we observed that many disordered manganese and cobalt oxide water oxidation catalysts directly oxidised peroxide in contrast to their more ordered analogues which catalysed its disproportionation i.e. MnO2 + 2H+ + H2O2 → Mn2+ + 2H2O + O2 (oxidation reaction) versus H2O2→ H2O + ½O2 (disproportionation reaction). By measuring the efficiency for one reaction over the other as a function of pH, we were able to quantify the relative stability of materials in two metal oxide series and thereby quantify their relative thermodynamic stability, "by proxy". We found that for the series of catalysts investigated the disorder made the materials stronger chemical oxidants and worse catalysts for the disproportionation of peroxide.

Item ID: 18968
Item Type: Article (Research - C1)
ISSN: 2192-6506
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A version of this publication was included as Chapter 3 of the following PhD thesis: King, Hannah (2019) The role of structural disorder in increasing the activity of cobalt oxide and manganese oxide water oxidation catalysts. PhD thesis, James Cook University, which is available Open Access in ResearchOnline@JCU. Please see the Related URLs for access.

Funders: Swinburne University (SU), James Cook University, Ministry of Higher Education, Iraq, Australian Government
Projects and Grants: SU Vice Chancellor's Women in STEM fellowship
Date Deposited: 28 Jun 2018 05:37
FoR Codes: 34 CHEMICAL SCIENCES > 3406 Physical chemistry > 340601 Catalysis and mechanisms of reactions @ 70%
34 CHEMICAL SCIENCES > 3406 Physical chemistry > 340608 Solution chemistry @ 30%
SEO Codes: 85 ENERGY > 8599 Other Energy > 859999 Energy not elsewhere classified @ 20%
97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 80%
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